Resistance variable memory device with sputtered metal-chalcogenide region and method of fabrication

ABSTRACT

A chalcogenide-based programmable conductor memory device and method of forming the device, wherein a chalcogenide glass region is provided with a plurality of alternating tin chalcogenide and metal layers proximate thereto. The method of forming the device comprises sputtering the alternating tin chalcogenide and metal layers.

This application is a continuation application of U.S. application Ser.No. 11/892,003, filed Aug. 17, 2007 now U.S. Pat. No. 7,433,227, whichis a divisional application of U.S. application Ser. No. 11/193,425,filed Aug. 1, 2005, now U.S. Pat. No. 7,274,034, issued Sep. 25, 2007,the disclosures of which are incorporated herein by reference in theirentirety.

FIELD OF THE INVENTION

The invention relates to the field of random access memory (RAM) devicesformed using a resistance variable material.

BACKGROUND

Resistance variable memory elements, which include chalcogenide-basedprogrammable conductor elements, have been investigated for suitabilityas semi-volatile and non-volatile random access memory devices. Atypical such device is disclosed, for example, in U.S. Pat. No.6,849,868 to Campbell, which is incorporated by reference.

In a typical chalcogenide-based programmable conductor memory device, aconductive material, such as silver, is incorporated into a chalcogenideglass. The resistance of the chalcogenide glass can be programmed tostable higher resistance and lower resistance states. An unprogrammedchalcogenide-based programmable conductor memory device is normally in ahigher resistance state. A write operation programs thechalcogenide-based programmable conductor memory device to a lowerresistance state by applying a voltage potential across the chalcogenideglass. The chalcogenide-based programmable conductor memory device maythen be read by applying a voltage pulse of a lesser magnitude thanrequired to program it; the resistance across the memory device is thensensed as higher or lower to define the ON and OFF states.

The programmed lower resistance state of a chalcogenide-basedprogrammable conductor memory device can remain intact for an indefiniteperiod, typically ranging from hours to weeks, after the voltagepotentials are removed. The chalcogenide-based programmable conductormemory device can be returned to its higher resistance state by applyinga reverse voltage potential of about the same order of magnitude as usedto write the device to the lower resistance state. Again, the higherresistance state is maintained in a semi- or non-volatile manner oncethe voltage potential is removed. In this way, such a device canfunction as a variable resistance memory having at least two resistancestates, which can define two respective logic states, i.e., at least abit of data.

One exemplary chalcogenide-based programmable conductor memory deviceuses a germanium selenide (i.e., Ge_(x)Se_(100-x)) chalcogenide glass asa backbone. The germanium selenide glass has, in the prior art,incorporated silver (Ag) and silver selenide (Ag₂Se).

Previous work by the inventor, Kristy A. Campbell, has been directed tochalcogenide-based programmable conductor memory devices incorporating asilver-chalcogenide material as a layer of silver selenide (e.g., Ag₂Se)or silver sulfide (e.g., Ag₂S) in combination with a silver-metal layerand a chalcogenide glass layer. The silver-chalcogenide materials aresuitable for assisting in the formation of a conducting channel throughthe chalcogenide glass layer for silver ions to move into to form aconductive pathway.

Tin (Sn) has a reduced thermal mobility in Ge_(x)Se_(100-x) compared tosilver and the tin-chalcogenides are less toxic than thesilver-chalcogenides, therefore tin-chalcogenides (e.g., SnSe) have alsobeen found to be useful in chalcogenide-based programmable conductormemory devices to replace silver selenide. However, sputtering of tinselenide to form such devices has proven difficult due to the increaseddensity of the sputtered layers. This increased density (e.g., ˜6 g/cm³sputtered compared to ˜3 g/cm³ evaporated) can prevent the motion ofsilver ions into the chalcogenide glass, thereby preventing the memorydevice from functioning. Therefore, evaporative deposition techniqueshave been used to deposit such material, which is generally a lessefficient, more costly, slower, and less controlled technique fordeposition. However, evaporation deposition of tin selenide and silveralso incorporates some oxygen into the resulting layer, which providesfor the lower density and allows for more mobility of silver ions.

SUMMARY

In an exemplary embodiment, the invention provides a chalcogenide-basedprogrammable conductor memory device having a layered stack with aregion containing tin-chalcogenide and silver proximate a chalcogenideglass layer. The device comprising a chalcogenide glass layer and theregion of tin-chalcogenide and silver is formed between two conductivelayers or electrodes. The tin-chalcogenide and silver region is formedby sputter deposition of tin-chalcogenide and silver.

In an exemplary embodiment of the invention, the chalcogenide-basedprogrammable conductor memory device contains alternating layers of tinselenide (e.g., Sn_(x)Se, where x is between about 0 and 2) and silver.

In an exemplary embodiment of the invention, the tin-chalcogenide andsilver region is formed by alternation of sputtering of tin selenide andsilver layers over the chalcogenide glass layer.

The above and other features and advantages of the invention will bebetter understood from the following detailed description, which isprovided in connection with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 show exemplary embodiments of memory devices in accordancewith the invention.

FIGS. 3-6 show exemplary sequential stages of processing during thefabrication of a memory device as in FIG. 2, in accordance with theinvention.

FIG. 7 shows an exemplary processor-based system incorporating a memorydevice in accordance with the invention.

DETAILED DESCRIPTION

In the following detailed description, reference is made to variousspecific embodiments of the invention. These embodiments are describedwith sufficient detail to enable those skilled in the art to practicethe invention. It is to be understood that other embodiments may beemployed, and that various structural, logical and electrical changesmay be made without departing from the spirit or scope of the invention.

The term “substrate” used in the following description may include anysupporting structure including, but not limited to, a semiconductorsubstrate that has an exposed substrate surface. A semiconductorsubstrate should be understood to include silicon, epitaxial silicon,silicon-on-insulator (SOI), silicon-on-sapphire (SOS), doped and undopedsemiconductors, epitaxial layers of silicon supported by a basesemiconductor foundation, and other semiconductor structures. Whenreference is made to a semiconductor substrate or wafer in the followingdescription, previous process steps may have been utilized to formregions or junctions in or over the base semiconductor or foundation.The substrate need not be semiconductor-based, but may be any supportstructure suitable for supporting an integrated circuit, including, butnot limited to, metals, alloys, glasses, polymers, ceramics, and anyother supportive materials as is known in the art.

The term “silver” is intended to include not only elemental silver, butsilver with other trace metals or in various alloyed combinations withother metals as known in the semiconductor industry, as long as suchsilver alloy is conductive, and as long as the physical and electricalproperties of the silver remain unchanged.

The term “tin” is intended to include not only elemental tin, but tinwith other trace metals or in various alloyed combinations with othermetals as known in the semiconductor industry, as long as such tin alloyis conductive, and as long as the physical and electrical properties ofthe tin remain unchanged.

The term “tin-chalcogenide” is intended to include various alloys,compounds, and mixtures of tin and chalcogens (e.g., sulfur (S),selenium (Se), tellurium (Te), polonium (Po), and oxygen (O)), includingsome species which have an excess or deficit of tin. For example, tinselenide, a species of tin-chalcogenide, is a preferred material for usein the invention and may be represented by the general formulaSn_(1+/−x)Se. Though not being limited by a particular stoichiometricratio between Sn and Se, devices of the present invention typicallycomprise an Sn_(x)Se species where x ranges between about 0 and about 2,e.g., SnSe.

The term “chalcogenide glass” is intended to include glasses thatcomprise at least one element from group VIA (also know as group 16) ofthe periodic table. Group VIA elements (e.g., O, S, Se, Te, and Po) arealso referred to as chalcogens.

The invention is now explained with reference to the figures, whichillustrate exemplary embodiments and throughout which like referencenumbers indicate like features. FIG. 1 shows an exemplary embodiment ofa memory device 100 constructed in accordance with the invention. Thedevice 100 shown in FIG. 1 is supported by a substrate 10. Over thesubstrate 10, though not necessarily directly so, is a conductiveaddress line 12, which serves as an interconnect for the device 100shown and a plurality of other similar devices of a portion of a memoryarray of which the shown device 100 is a part. It is possible toincorporate an optional insulating layer (not shown) between thesubstrate 10 and address line 12, and this may be preferred if thesubstrate 10 is semiconductor-based.

The conductive address line 12 can be any material known in the art asbeing useful for providing an interconnect line, such as dopedpolysilicon, silver (Ag), gold (Au), copper (Cu), tungsten (W), nickel(Ni), aluminum (Al), platinum (Pt), titanium (Ti), and other materials.Over the address line 12 is a first electrode 16, which can be definedwithin an insulating layer 14, if desired, and which is also over theaddress line 12. This electrode 16 can be any conductive material thatwill not migrate into chalcogenide glass, but is preferably tungsten(W). The insulating layer 14 should not allow the migration of silver(or other metal, e.g., copper) ions and can be an insulating nitride,such as silicon nitride (Si₃N₄), a low dielectric constant material, aninsulating glass, or an insulating polymer, but is not limited to suchmaterials.

A memory element, i.e., the portion of the memory device 100 whichstores information, is formed over the first electrode 16. In theembodiment shown in FIG. 1, a layer of chalcogenide glass 18, preferablya germanium chalcogenide such as germanium selenide (Ge_(x)Se_(100-x)),can be provided over the first electrode 16. The germanium selenide canbe within a stoichiometric range of about Ge₂₀Se₈₀ to about Ge₄₃Se₅₇,preferably about Ge₄₀Se₆₀, i.e., Ge₂Se₃. The layer of chalcogenide glass18 can be between about 100 Å and about 1000 Å thick, preferably about300 Å thick. Layer 18 need not be a single layer of glass, but may alsobe comprised of multiple sub-layers of chalcogenide glass having thesame or different stoichiometries. This layer of chalcogenide glass 18is in electrical contact with the underlying electrode 16.

Over the chalcogenide glass layer 18 is a region 20 of tin-chalcogenide,preferably tin selenide (Sn_(x)Se, where x is between about 0 and 2),and silver, which are layered as shown in FIG. 14. Alternating layers oftin selenide and silver are utilized to provide a region 20incorporating both materials, wherein the silver is dispersed throughoutthe tin selenide. It is also possible that other chalcogenide materialsmay be substituted for selenium here, such as sulfur, oxygen, ortellurium; however, selenium is preferred and the remainder of thedescription will describe the invention utilizing tin selenide. The tinselenide and silver region 20 is preferably about 1,000 Å to about 2,000Å thick; however, its thickness depends, in part, on the thickness ofthe underlying chalcogenide glass layer 18. The ratio of the thicknessof the tin selenide and silver region 20 to that of the underlyingchalcogenide glass layer 18 can be at least about 1:1, preferably about3.33:1 to about 6.67:1.

Still referring to FIG. 1, over the tin selenide and silver region 20 isa second electrode 24. The second electrode 24 can be made of the samematerial as the first electrode 16, but is not required to be so. In theexemplary embodiment shown in FIG. 1, the second electrode 24 ispreferably tungsten (W). The device(s) may be isolated by an insulatinglayer 26. The memory device 100 shown in FIG. 1 is a simplifiedexemplary embodiment of the invention. Other alternative embodiments mayhave more glass layers, as shown, for example, in FIG. 2, or may beprovided within a via or may be made of blanket layers over an electrodesuch as electrode 16. Also, alternative embodiments may provide a commonelectrode in place of the dedicated electrode 16, shown in FIG. 1.

In accordance with the embodiment shown at FIG. 1, in a completed memorydevice 100, the tin selenide and silver region 20 provides a source oftin selenide and silver, which is incorporated into chalcogenide glasslayer 18 during a conditioning step after formation of the memory device100. The tin selenide and silver region 20 may also provide silverselenide (Ag₂Se) and silver tin selenide (Ag_(x)Sn_(y)Se_(z)) tocondition the chalcogenide glass layer 18. Specifically, theconditioning step comprises applying a potential across the memoryelement structure of the device 100 such that material from the region20 is incorporated into the chalcogenide glass layer 18, thereby forminga conducting channel in the chalcogenide glass layer 18. Movement ofsilver ions into or out of the conducting channel during subsequentprogramming respectively forms or dissolves a conductive pathway, whichcauses a detectible resistance change across the memory device 100.

FIG. 2 shows another exemplary embodiment of a memory device 101constructed in accordance with the invention. Memory device 101 has manysimilarities to memory device 100 of FIG. 1 and layers designated withlike reference numbers are preferably the same materials and have thesame thicknesses as those described in relation to the embodiment shownin FIG. 1. The primary difference between device 100 and device 101 isthe addition to device 101 of an optional second chalcogenide glasslayer 18 a, a metal layer 22, and an optional third chalcogenide glasslayer 18 b.

The optional second chalcogenide glass layer 18 a is formed over the tinselenide and silver region 20, is preferably Ge₂Se₃, and is preferablyabout 150 Å thick. Over this optional second chalcogenide glass layer 18a is a metal layer 22, which is preferably silver (Ag) and is preferablyabout 500 Å thick. Over the metal layer 22 is an optional thirdchalcogenide glass layer 18 b, which is preferably Ge₂Se₃ and ispreferably about 100 Å thick. The optional third chalcogenide glasslayer 18 b provides an adhesion layer for subsequent electrodeformation. As with layer 18 of FIG. 1, layers 18 a and 18 b are notnecessarily a single layer, but may be comprised of multiple sub-layers.Additionally, the optional second and third chalcogenide layers 18 a and18 b may be a different chalcogenide glass from the first chalcogenideglass layer 18 or from each other.

Over the optional third chalcogenide glass layer 18 b is a secondelectrode 24, which may be any conductive material, but is preferablynot one that will migrate into the memory element stack and alter memoryoperation (e.g., not Cu or Ag), as discussed above for the precedingembodiments. Preferably, the second electrode 24 is tungsten (W).

FIGS. 3-6 illustrate a cross-sectional view of a wafer during thefabrication of a memory device 101 as shown by FIG. 2. Although theprocessing steps shown in FIGS. 3-6 most specifically refer to memorydevice 101 of FIG. 2, the methods and techniques discussed may also beused to fabricate other memory device structures, such as shown in FIG.1, as would be understood by a person of ordinary skill in the art basedon a reading of this specification.

As shown by FIG. 3, a substrate 10 is provided. As indicated above, thesubstrate 10 can be semiconductor-based or another material useful as asupporting structure for an integrated circuit, as is known in the art.If desired, an optional insulating layer (not shown) may be formed overthe substrate 10; the optional insulating layer may be silicon nitrideor other insulating materials used in the art. Over the substrate 10 (oroptional insulating layer, if desired), a conductive address line 12 isformed by depositing a conductive material, such as doped polysilicon,aluminum, platinum, silver, gold, nickel, but preferably tungsten,patterning one or more conductive lines, for example, withphotolithographic techniques, and etching to define the address line 12.The conductive material maybe deposited by any technique known in theart, such as sputtering, chemical vapor deposition, plasma enhancedchemical vapor deposition, evaporation, or plating.

Still referring to FIG. 3, over the address line 12 is formed aninsulating layer 14. This layer 14 can be silicon nitride, a lowdielectric constant material, or many other insulators known in the artthat do not allow silver ion migration, and may be deposited by anymethod known in the art. An opening 14 a in the insulating layer ismade, for example, by photolithographic and etching techniques, therebyexposing a portion of the underlying address line 12. Over theinsulating layer 14, within the opening 14 a, and over the address line12 is formed a conductive material, preferably tungsten (W). A chemicalmechanical polishing (CMP) step may then be utilized, using theinsulating layer 14 as a stop, to remove the conductive material fromover the insulating layer 14, to leave it as a first electrode 16 overthe address line 12, and planarize the wafer.

FIG. 4 shows the cross-section of the wafer of FIG. 3 at a subsequentstage of processing. A series of layers making up the memory device 101(FIG. 2) are blanket-deposited over the wafer. A chalcogenide glasslayer 18 is formed to a preferred thickness of about 300 Å over thefirst electrode 16 and insulating layer 14. The chalcogenide glass layer18 is preferably Ge₂Se₃. Deposition of this chalcogenide glass layer 18may be accomplished by any suitable method, such as evaporativetechniques or chemical vapor deposition using germanium tetrahydride(GeH₄) and selenium dihydride (SeH₂) gases; however, the preferredtechnique utilizes either sputtering from a germanium selenide targethaving the desired stoichiometry or co-sputtering germanium and seleniumin the appropriate ratios.

Still referring to FIG. 4, the tin selenide and silver region 20 isformed over the chalcogenide glass layer 18. To form region 20,alternating layers of tin selenide 20 a and silver 20 b are deposited bysputtering. Each tin selenide layer 20 a is preferably between about 200Å and about 400 Å. Each silver layer 20 b is preferably between about 50Å and about 100 Å. Sputtering these layers is preferred to evaporationdeposition because of the increased efficiency, cost effectiveness,speed of fabrication, control of deposition rate, control of layerthickness, and control of layer properties provided by sputtering.Although the sputtered tin selenide and silver region 20 is denser thana like evaporated region, the proximity of the silver and the tinselenide layers 20 b and 20 a, respectively, allows for mixing andmigration of these materials, heretofore not available to such sputteredregions.

Again, the thickness of region 20 is selected based, in part, on thethickness of layer 18; therefore, where the chalcogenide glass layer 18is preferably about 300 Å thick, the alternating tin selenide layers 20a and silver layers 20 b should make for a region 20 that is about 1,000Å to about 2,000 Å thick. It should be noted that, as the processingsteps outlined in relation to FIGS. 3-6 may be adapted for the formationof other devices in accordance the invention.

Still referring to FIG. 4, a second chalcogenide glass layer 18 a isformed over the tin selenide and silver region 20, which can besputtered similarly to the formation of layer 18. The secondchalcogenide glass layer 18 a is preferably a germanium selenide layerwith a stoichiometry of Ge₂Se₃ and is preferably about 150 Å thick. Overthe second chalcogenide glass layer 18 a, a metal layer 22 is formed.The metal layer 22 is preferably silver (Ag), or at least containssilver, and is formed to a preferred thickness of about 500 Å. The metallayer 22 may be deposited by any technique known in the art. A thirdchalcogenide glass layer 18 b is formed over the metal layer 22. Thisthird chalcogenide glass layer 18 b is also preferably germaniumselenide with a stoichiometry of Ge₂Se₃, can be about 100 Å thick, andis preferably deposited by sputtering.

Still referring to FIG. 4, over the third chalcogenide glass layer 18 b,a conductive material is deposited to form a second electrode 24 layer.Again, this conductive material may be any material suitable for aconductive electrode, but is preferably tungsten; however othermaterials may be used such as titanium nitride or tantalum, for example.

Now referring to FIG. 5, a layer of photoresist 30 is deposited over thetop electrode 24 layer, masked and patterned to define the stacks forthe memory device 101, which is one of a plurality of like memorydevices of a memory array. An etching step is used to remove portions oflayers 18, 20 a, 20 b, 18 a, 22, 18 b, and 24, with the insulating layer14 used as an etch stop, leaving stacks as shown in FIG. 5. Thephotoresist 30 is removed, leaving a substantially complete memorydevice 101, as shown by FIG. 6. An insulating layer 26 may be formedover the device 101 to achieve a structure as shown by FIG. 2. Thisisolation step can be followed by the forming of connections to othercircuitry of the integrated circuit (e.g., logic circuitry, senseamplifiers, etc.) of which the memory device 101 is a part, as is knownin the art.

A conditioning step is performed by applying a voltage pulse of a givenduration and magnitude to incorporate material from the tin selenide andsilver region 20 into the chalcogenide glass layer 18 to form aconducting channel in the chalcogenide glass layer 18. The conductingchannel will support a conductive pathway during operation of the memorydevice 101, the presence or lack of which provides at least twodetectable resistance states for the memory device 101.

The embodiments described above refer to the formation of only a fewpossible chalcogenide-based programmable conductor memory device inaccordance with the invention, which may be part of a memory array. Itmust be understood, however, that the invention contemplates theformation of other memory structures within the spirit of the invention,which can be fabricated as a memory array and operated with memoryelement access circuits.

FIG. 7 illustrates a processor system 400 which includes a memorycircuit 448 employing chalcogenide-based programmable conductor memorydevices (e.g., device 100 and 101) fabricated in accordance with theinvention. A processor system, such as a computer system, generallycomprises a central processing unit (CPU) 444, such as a microprocessor,a digital signal processor, or other programmable digital logic devices,which communicates with an input/output (I/O) device 446 over a bus 452.The memory circuit 448 communicates with the CPU 444 over bus 452,typically through a memory controller.

In the case of a computer system, the processor system may includeperipheral devices, such as a floppy disk drive 454 and a compact disc(CD) ROM drive 456, which also communicate with CPU 444 over the bus452. Memory circuit 448 is preferably constructed as an integratedcircuit, which includes one or more resistance variable memory devices,e.g., device 101. If desired, the memory circuit 448 may be combinedwith the processor, for example CPU 444, in a single integrated circuit.

The above description and drawings should only be consideredillustrative of exemplary embodiments that achieve the features andadvantages of the invention. Modification and substitutions to specificprocess conditions and structures can be made without departing from thespirit and scope of the invention. Accordingly, the invention is not tobe considered as being limited by the foregoing description anddrawings, but is only limited by the scope of the appended claims.

1. A memory device, comprising: a first electrode; a chalcogenide glassmaterial formed over said first electrode; a tin chalcogenide materialformed over said chalcogenide glass material; a first silver materialformed over said tin chalcogenide material; a second silver materialformed below said tin chalcogenide material; and a second electrodeformed over said first electrode, said chalcogenide glass material, saidtin chalcogenide material, said first silver material and said secondsilver material.
 2. The memory device of claim 1, wherein said tinchalcogenide material comprises tin selenide.
 3. The memory device ofclaim 1, wherein said chalcogenide glass material comprises germaniumselenide.
 4. The memory device of claim 3, wherein said germaniumselenide has a stoichiometry of Ge₂Se₃.
 5. The memory device of claim 1,further comprising a plurality of alternating tin chalcogenide layersand silver layers, said plurality of alternating tin chalcogenide layersand silver layers forming a region between about 1,000 Å and about 2,000Å thick.
 6. The memory device of claim 1, wherein the ratio of thethickness of said tin chalcogenide material and each of said firstsilver material and said second silver material is between about 3.33:1and 6.67:1.
 7. The memory device of claim 1, further comprising: asecond chalcogenide glass material formed over said tin chalcogenidematerial, said first silver material and said second silver material; ametal material formed over said second chalcogenide glass material; anda third chalcogenide glass material formed over said metal material. 8.The memory device of claim 7, wherein said second chalcogenide glasslayer is about 150 Å thick and said third chalcogenide glass layer isabout 100 Å thick.
 9. The memory device of claim 7, wherein said metallayer is about 500 Å thick.
 10. The memory device of claim 1, whereinsaid memory device is part of a processor system, further comprising: aprocessor and memory circuit, wherein said memory circuit comprises saidmemory device.
 11. The memory device of claim 1, wherein saidchalcogenide glass material further comprises a plurality of sub-layersof chalcogenide glass material each having different stoichiometricproperties.
 12. The memory device of claim 1, wherein said chalcogenideglass material further comprises a plurality of sub-layers ofchalcogenide glass material each having the same stoichiometricproperties.
 13. The memory device of claim 1, further comprising: asecond chalcogenide glass material formed over said tin chalcogenidematerial, said first silver material and said second silver material; ametal material formed over said second chalcogenide glass material; anda third chalcogenide glass material formed over said metal material. 14.The memory device of claim 1, wherein said second chalcogenide glassmaterial and said third chalcogenide glass material are each made from adifferent chalcogenide glass than said first chalcogenide glassmaterial.
 15. A method of forming a memory device, comprising: forming achalcogenide glass layer over a first electrode; forming a tinchalcogenide layer over said chalcogenide glass layer; forming a firstsilver layer over said tin chalcogenide layer; forming a second silverlayer below said tin chalcogenide layer; and forming a second electrodeover said first electrode, said chalcogenide glass layer, said tinchalcogenide layer, said first silver layer and said second silverlayer.
 16. The method of claim 15, further comprising forming aplurality of sub-layers of chalcogenide glass within said chalcogenideglass layer.
 17. The method of claim 15, further comprising: forming asecond chalcogenide glass layer over said tin chalcogenide layer, saidfirst silver layer and said second silver layer; forming a metal layerover said second chalcogenide glass layer; and forming a thirdchalcogenide glass layer over said metal layer.
 18. The method of claim17, wherein said second chalcogenide glass layer and said thirdchalcogenide glass layer are each formed of a different chalcogenideglass than said first chalcogenide glass layer.
 19. The method of claim17, wherein said second chalcogenide glass layer and said thirdchalcogenide glass layer are each formed of the same chalcogenide glassas said first chalcogenide glass layer.
 20. The method of claim 15,wherein said first electrode is formed of tungsten.